Studies On C-H Bond Functionlization Adjacent To The Nitrogen Of Tertiary Amines And Cascade Cyclization Reaction Of O-Alkynylanilines

Some researches have been done in the field of ortho functionalization of nitrogen atom of tertiary amines and tandem cyclization of alkynes, and mainly includes the following four parts:Part Ⅰ:Pt-catalyzed ortho oxidative dehydrogenation reaction of nitrogen atom of the tertiary amines1. The imine was formed by the platinum-catalyzed ortho oxidative dehydrogenation of tertiary amine, and the imine went through intramolecular rearrangement to generate the enamine, which underwent Michael addition with nitroolefins; The enamines generated in situ can also undergo Michael addition/cyclization reaction with the o-hydroxy-nitroolefins to generate a series of nitrogen-containing heterocyclic compounds.2. After achieveing intermolecular Michael addition, we further studied in situ generated enamines undergone aldol condensation reaction with the aldehyde. The salicylaldehyde was introduced into the reaction, and the results meant the coumarin derivatives were obtained by the ring opening and condensation cyclization.Part Ⅱ:Pt-catalyzed the ortho [1,5]-H migration reaction of nitrogen atom of the tertiary aminesThe propargylic esters experienced3,3-ester group migration to in-situ generate allenes under Pt-catalysis, since there was part of the electricity in the1,3-linked of allenes, which can accept negative hydrogen offensive. Under the driven of the nitrogen atoms and the pull of allens, tertiary amines underwent intramolecular [1,5]-H migration and intramolecular ring closure to generate quinoline derivatives.Part Ⅲ:The Lewis acid scandium catalyzed intramolecular ring opening of the cyclopropane and tandem cyclization reactionLewis acid catalyzed the cyclopropane went through ring opening to form1,3dipoles, which underwent intramolecular [3+2] cycloaddition reaction with alkynes, and stereoselectively generated the cyclopentyl vinyl compounds.Part Ⅳ:palladium/copper catalyzed intramolecular tandem cyclization and oxidative reaction 1. A copper-catalyzed intramolecular enyne cyclization reaction was occurred using oxygen as oxidant to synthesize a series of quinoline derivatives.2. Palladium/copper catalyzed o-alkynyl aniline first underwent intramolecular cyclization in-situ to generate the indole, which went through tandem addition/cyclization reaction with arylalkynyl to generate multi-substituted indole compounds.3. Palladium/copper co-catalyzed o-alkynyl aniline underwent intramolecular oxidative cyclization to produce3-acyl indole. Tert-butyl hydroperoxide (TBHP) acts not only as the oxidant, but also as reactants.